Fluoroalkyloxy dispersant

ABSTRACT

The present invention provides a compound according to the formula: CH 2 ═C(R 1 )—C(O)—R 6 —NHCO 2 (CH 2 ) p (CF 2 ) q —O—((CF 2 ) a CFXO) m (CF 2 ) r —Z wherein each R 1  is independently selected from —H, —CH 3 , —F and —Cl, wherein each R 6  is independently selected from substituted or unsubstituted C1-C10 alkyl, cyclic alkyl, or aryl groups, wherein each a is independently selected from 0-3, wherein each X is independently selected from —F, —CF 3  or —CF 2 CF 3 , wherein each p is independently selected from 1-4, each q is independently selected from 1-5, each r is independently selected from 1-5, each m is independently selected from 1-50, each Z is independently selected from —F and —(CH 2 ) s OH, and each s is independently selected from 1-4. The present invention also provides for the use of this compound as a surfactant in highly fluorinated liquid solvents. Latexes of dispersed particles utilizing this surfactant are provided.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is a divisional of U.S. application Ser. No.09/605,211, filed Jun. 28, 2000, now allowed, the disclosure of which isherein incorporated by reference.

FIELD OF THE INVENTION

[0002] This invention relates to a compound useful as a dispersant inhighly fluorinated solvents. The compound contains an ethylenic doublebond by which it may be joined to another moiety, e.g. by free-radicalpolymerization. The compound is described by the formula:CH₂═C(R¹)—C(O)—R⁶—NHCO₂(CH₂)_(p)(CF₂)_(q)—O—((CF₂)_(a)CFXO)_(m)(CF₂)_(r)—Zwherein each R¹ is independently selected from —H, —CH₃, —F and —Cl,wherein each R⁶ is independently selected from substituted orunsubstituted C1-C10 alkyl, cyclic alkyl, or aryl groups, wherein each ais independently selected from 0-3, wherein each X is independentlyselected from —F, —CF₃ or —CF₂CF₃, wherein each p is independentlyselected from 1-4, each q is independently selected from 1-5, each r isindependently selected from 1-5, each m is independently selected from1-50, each Z is independently selected from —F and —(CH₂)_(s)OH, andeach s is independently selected from 1-4.

BACKGROUND OF THE INVENTION

[0003] U.S. Pat. No. 5,397,669 (Minnesota Mining & Manufacturing)discloses liquid toners for use with perfluorinated solvents. The patentdiscloses that the compositions are film-forming, allowing them tofunction properly as toners. ('669 at p. 8 lns. 3-5). The '669 patentdiscloses pigment particles bound to a polymer that is highlyfluorinated in specific parts, and that includes monomer units havinggroups that bind polyvalent metal ions. The '669 patent also disclosespigment particles bound to a polymer that is highly fluorinated in itsentirety, without requiring monomers having groups that bind polyvalentmetal ions.

[0004] U.S. Pat. No. 5,530,053 (Minnesota Mining & Manufacturing) alsodiscloses liquid toners for use with perfluorinated solvents. The tonersof '053 are polymeric dyes which are highly fluorinated in specifiedparts and have attached chromophoric groups. The '053 patent disclosesthat the toner can form a latex in perfluorinated solvent, where thetoner takes a core-shell form with the hydrocarbon portion in the coreand the fluorocarbon portion in the shell.

[0005] U.S. Pat. No. 5,919,293 (Hewlett-Packard) discloses ink jet inkscomposed of colorants in Fluorinert™ solvents (Minnesota Mining &Manufacturing Co., St. Paul, Minn.), which are perfluorinated ornearly-perfluorinated alkanes.

[0006] U.S. Pat. No. 5,573,711 (Copytele) discloses the use of certainpolymeric fluorosurfactants in electrophoretic image displays. The '711patent teaches the use of Fluorad™ surfactants (Minnesota Mining &Manufacturing Co., St. Paul, Minn.), including FC-171, having thestructure R_(f)—SO₂N(C₂H₅)(CH₃CH₃O)_(n)CH₃, where n is about 8 and R_(f)is a fluorocarbon portion.

SUMMARY OF THE INVENTION

[0007] Briefly, the present invention provides a compound according tothe formula:CH₂═C(R¹)—C(O)—R⁶—NHCO₂(CH₂)_(p)(CF₂)_(q)—O—((CF₂)_(a)CFXO)_(m)(CF₂)_(r)—Z,wherein each R¹ is independently selected from —H, —CH₃, —F and —Cl,wherein each R⁶is independently selected from substituted orunsubstituted C1-C10 alkyl, cyclic alkyl, or aryl groups, wherein each ais independently selected from 0-3, wherein each X is independentlyselected from —F, —CF₃ or —CF₂CF₃, wherein each p is independentlyselected from 1-4, each q is independently selected from 1-5, each r isindependently selected from 1-5, each m is independently selected from1-50, each Z is independently selected from —F and —(CH₂)_(s)OH, andeach s is independently selected from 1-4. Preferably each m isindependently selected from 7-15. Preferably Z is —(CH₂)_(s)OH.Preferably a, p, q, r and s are each 1 and wherein X is —F.

[0008] In another aspect, the present invention provides a secondcompound which is a reaction product of the compound above resultingfrom free-radical addition to the ethylenic double bond. In particular,a non-film-forming latex of particles comprising the compound above in ahighly fluorinated solvent is provided.

[0009] What has not been described in the art, and is provided by thepresent invention, is a reactive dispersant according to the presentformula and its use in a non-film-forming latex ofhydrocarbon/fluorocarbon particles dispersed in a fluorocarbon solventuseful in an electrophoretic display.

[0010] In this application:

[0011] “reacting dyes” means dyes which are covalently bound to thepolymer;

[0012] “non-reacting dyes” means dyes which are not substantiallyincorporated into a polymer by polymerization, including every dye thatis not a reacting dye;

[0013] “highly fluorinated”, means containing fluorine in an amount of40 wt % or more, but preferably 50 wt % or more and more preferably 60wt % or more, and refers to the fluorine content of a population ofchemical moieties where applicable, such as in the term, “one or morehighly fluorinated macromers”;

[0014] “non-fluorinated”, means containing substantially no fluorine,i.e. containing fluorine in an amount of 5 wt % or less, but preferably1 wt % or less and most preferably 0 wt %, and refers to the fluorinecontent of a population of chemical moieties where applicable, such asin the term, “one or more non-fluorinated free-radically-polymerizablemonomers”;

[0015] “C(number)” refers to a chemical moiety containing the indicatednumber of carbon atoms;

[0016] “(meth)acrylate” means acrylate and methacrylate; and

[0017] “substituted” means, for a chemical species, substituted byconventional substituents which do not interfere with the desiredproduct or process, e.g., substituents can be alkyl, alkoxy, aryl,phenyl, halo (F, Cl, Br, I), cyano, etc.

[0018] It is an advantage of the present invention to provide adispersant for use in highly fluorinated solvents and which isparticularly useful in making a latex of non-film-forming dye-bearingparticles.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0019] The present invention provides a compound according to theformula:CH₂═C(R¹)—C(O)—R⁶—NHCO₂(CH₂)_(p)(CF₂)_(q)—O—((CF₂)_(a)CFXO)_(m)(CF₂)_(r)(CH₂)_(s)OH,wherein each R¹ is independently selected from —H, —CH₃, —F and Cl,wherein each R⁶ is independently selected from substituted orunsubstituted C1-C10 alkyl, cyclic alkyl, or aryl groups, wherein each ais independently selected from 0-3, wherein each X is independentlyselected from —F, —CF₃ or —CF₂CF₃, wherein each p is independentlyselected from 1-4, each q is independently selected from 1-5, each r isindependently selected from 1-5, each s is independently selected from1-4, each m is independently selected from 1-50. Preferably each m isindependently selected from 7-15. Preferably a, p, q, r and s are each 1and wherein X is —F.

[0020] A non-film-forming latex employing the dispersant according tothe present invention comprises a highly fluorinated liquid solvent anddispersed particles comprising a polymer comprising units according toformula I:

[0021] wherein each (fcp) is independently selected from highlyfluorinated polymer chains which may terminate at the —A=group ofanother unit according to formula I so as to form a polymer moleculethat contains two or more A groups linked by (fcp) groups; wherein eachQ is independently selected from —H and straight or branchednon-fluorinated polymer chains (hcp), wherein no more than one Q of eachunit according to formula I may be —H, and wherein each (hcp) mayterminate at the —A=group of another unit according to formula I so asto form a polymer molecule that contains two or more A groups linked by(hcp) groups. Preferably some of the (hcp) groups are branched due tothe inclusion of polyfunctional crosslinkers. Preferably the particlescontain reacting or non-reacting dyes. Preferably the particlesadditionally contain charging agents.

[0022] Preferably the —A=group is the moiety according to formula II:

[0023] wherein each R¹ is independently selected from —H, —CH₃, —F and—Cl; wherein each —R⁶— is independently selected from divalentsubstituted or unsubstituted C1-C10 alkylene, cyclic alkylene, orarylene groups. The (fcp) moieties may terminate at A groups at one orboth ends. The (hcp) moieties may terminate at A groups at one or bothends, or at more than two ends if the (hcp) moiety is branched due tothe inclusion of a crosslinker. Thus it is contemplated that a singlemolecule may contain numerous A groups linked by (hcp) groups.

[0024] The fluorocarbon polymer (fcp) portions are preferably highlyfluorinated macromers. Preferred macromers include macromers of monomersselected from fluoroalkyl acrylates, fluoroalkyl methacrylates,fluoroalkyl haloacrylates and fluoroalkyl halomethacrylates. Preferablythese macromers are fluoropolymer chains comprising units according toformula III:

[0025] where each R¹ is independently selected from —H, —CH₃, —F and—Cl; each n is independently selected from integers from 1 to 10; andeach R² is selected independently from: highly fluorinated substitutedor unsubstituted C1-C20 alkyl, cyclic alkyl, or aryl groups;—N(R³)SO₂R⁴, where each —R³ is selected independently from —H andsubstituted or unsubstituted C1-C8 alkyl, and where each —R⁴ is selectedindependently from highly fluorinated substituted or unsubstitutedC1-C20 alkyl, cyclic alkyl, or aryl groups. Preferably —R¹ groups are —Hor —CH₃. Preferably n is 1 or 2, more preferably 1. Preferably —R² is ahighly fluorinated C1-C20 alkyl group, more preferably a highlyfluorinated C1-C8 alkyl group. In another preferred embodiment, the —R²groups of the (fcp) are a mixture selected from highly fluorinated C1-C8alkyl groups and —N(R³)SO₂R⁴, where —R³ is selected from C1-C8 alkylgroups —R⁴ is selected from highly fluorinated C1-C8 alkyl groups.

[0026] In another preferred embodiment, (fcp) arepolyfluoroalykylethers, preferably those comprising one or more unitsaccording to the formula —(CF₂)_(a)CFXO—, where a is 0-3, but mostpreferably 1, and X is —F, —CF₃ or —CF₂CF₃ but most preferably —F. Morepreferred polyfluoroalykylethers comprise units according to the formula—CF₂CF₂O—. Preferred polyfluoroalykylethers are those according to theformula —NHCO₂(CH₂)_(p)(CF₂)_(q)—O—(CF₂CF₂O)_(m)(CF₂)_(r)(CH₂)_(s)OHwhen (fcp) is monovalent or—NHCO₂(CH₂)_(p)(CF₂)_(q)—O—(CF₂CF₂O)_(m)(CF₂)_(r)(CH₂)_(s)CO₂NH— when(fcp) is divalent, where p is 1-4, q is 1-5, r is 1-5, s is 1-4, m is1-50. Preferably p is 1-2. Preferably q is 1-2. Preferably r is 1-2.Preferably s is 1-2. Preferably p is equal to s and q is equal to r.Preferably m is 5-20 and more preferably 7-15. The chain may alternatelyterminate with —F in place of —(CH₂)_(s)OH in the formula above.

[0027] The hydrocarbon polymer (hcp) groups are preferablynon-fluorinated macromers (including co-macromers) of (meth)acrylate andother ethylenically unsaturated monomers such as styrenes. Thehydrocarbon polymer (hcp) macromers are preferably polymers orcopolymers of one or more of the following preferred monomers. Preferredmonomers include monomers according to the formula: CH₂═CR¹—C(O)OR²,where —R¹ is hydrogen or methyl and —R² is selected from C1-C20substituted or unsubstituted, straight-chain or branched or cyclic,alkyl or aryl groups. Especially preferred monomers of this groupinclude ethyl (meth)acrylate, methyl (meth)acrylate and isobornyl(meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl(meth)acrylate, hydroxypropyl (meth)acrylate, acetoacetoxyethyl(meth)acrylate. Preferred monomers also include styrene or substitutedstyrene monomers such as methylstyrene.

[0028] The hydrocarbon polymer (hcp) portions preferably includenon-fluorinated crosslinkers, and are therefore branched. Preferredcrosslinkers include polyacrylates such as PEG Diacrylate with amolecular weight of preferably between 200 and 2000.

[0029] In order to improve resistance to film-forming, preferably the(hcp) portion of the particles contains one or more of: crosslinkers,cyclic or polycyclic monomers, aromatic monomers, and C12 or largersubstituted or unsubstituted alkyl monomers. More preferably the (hcp)portion of the particles contains one or more of: crosslinkers, cyclicor polycyclic monomers and aromatic monomers.

[0030] The hydrocarbon polymer (hcp) portions may also include reactingdyes which are incorporated into the polymer chain as monomer units.Such reacting dyes contain a chromogenic portion and a reactive portion,which are not exclusive of each other. Preferably the reactive portionis a free-radically-polymerizable group, such as a vinyl or(meth)acrylate group. In one preferred embodiment, afree-radically-polymerizable group is added to a dye by derivatizationwith isocyanatoethyl methacrylate. In one procedure, the dye issuspended in a solvent such as FC-75 by sonication and an equivalent ofisocyanatoethyl methacrylate is added dropwise, followed by two drops ofdibutyltin dilaurate catalyst and continued sonication and agitation for1 hour. A preferred reacting dye and method of preparation is disclosedin the examples below.

[0031] The dispersed particles may also include non-reacting dyes. Thenon-reacting dyes have greater affinity for the particles than for thesolvent and are therefore contained in the particles. Preferably thenon-reacting dyes have greater affinity for the (hcp) portions of theparticle than for the (fcp) portions or the solvent. Preferrednon-reacting dyes are disclosed in the examples below. The particlesaccording to the present invention preferably contain no particulatepigments.

[0032] Without wishing to be bound by theory, it is believed that theparticles take the form of a hydrocarbon-polymer-rich core and afluoropolymer-rich shell. It is believed that most dyes are incorporatedin the core due to compatibility with the hydrocarbon material of thecore. Thus it is believed that reducing the fluoropolymer content of theparticles improves the optical properties of the particle by allowingeasier access to the dyed core. In addition, it is believed thatreducing the fluoropolymer content of the particles can improve theparticle's resistance to film formation. Preferably the particles arecomposed of 40-99 percent by weight non-fluorinated hydrocarbon polymerand 1-60 percent by weight highly fluorinated fluoropolymer. Morepreferably the particles are composed of 60-99 percent by weightnon-fluorinated hydrocarbon polymer. More preferably the particles arecomposed of 1-40 percent by weight highly fluorinated fluoropolymer.Most preferably the particles are composed of 1-10 percent by weighthighly fluorinated fluoropolymer. However, greater fluoropolymer contentis acceptable as particle size is decreased. In particles of less than200 nm average diameter, the particles are preferably composed of 10-40percent by weight highly fluorinated fluoropolymer, more preferably10-25 percent by weight highly fluorinated fluoropolymer.

[0033] The dispersed particles may also include charging agents. Thecharging agent renders the particle mobile under the influence of anelectric field. In addition, the charge imparted to the particles by thecharging agent creates an electrostatic repulsion between particleswhich improves resistance to film formation. Like non-reacting dyes, thecharging agent has a greater affinity for the particles than for thesolvent and is therefore contained in the particles. Preferably thecharging agent has a greater affinity for the (hcp) portions of theparticle than for the (fcp) portions or the solvent. The charging agentis preferably cationic, more preferably a quaternary ammonium cation.Preferred charging agents include 1-ethyl-3-methyl-1H-imidazoliumbis(trifluoromethylsulfonylamide), which may be prepared as disclosed inthe examples below; (C₄H₉)₃N:HOC(O)—C₇F₁₅; (C₃H₇)₄N⁺ ⁻OC(O)—C₇F₁₅;(C₄H₉)₄N⁺ ⁻OC(O)—C₉F₁₉; C₇F₁₅—CO₂H; and combinations thereof.

[0034] Latexes according to the present invention preferably demonstratea high conductance as measured by the method described in the examplesbelow. Measured conductance is taken to reflect the charge/mass ratio(charge density) of the particles in suspension, whether imparted by thecharging agent or inherent in the particle itself. Preferred latexesaccording to the present invention have a conductance of 1 picomho/cm ormore, more preferably 4 picomho/cm or more, and most preferably 9picomho/cm or more. However, lower conductance is acceptable whenparticle size is decreased. In particles of less than 200 nm averagediameter, conductance is preferably 0.1 picomho/cm or more.

[0035] The average diameter (particle size) for the dispersed particlesof the latex is preferably measured by the method described in theexamples below. Smaller particles are preferred for a number of reasons,including greater and faster mobility and lesser tendency to form afilm. Preferably the particles have an average diameter of 1000 nm orless, more preferably 350 nm or less, more preferably 300 nm or less,more preferably 250 nm or less, and most preferably 200 nm or less. Theseed method of latex formation described below has been found to produceexceptionally fine particles. That method and the resulting fineparticles are preferred.

[0036] The solvent may be any suitable highly fluorinated solvent. Thesolvent is preferably a fluorocarbon, especially a branched orunbranched, cyclic or non-cyclic fluoroalkane. Preferred solventsinclude FLUORINERT™ fluorinated solvents available from 3M Company, St.Paul, Minn. Two especially preferred solvents are FLUORINERT FC-75, aperfluorinated C₈ solvent, CAS No. [86508-42-1], and FLUORINERT FC-84, aperfluorinated C₇ solvent, CAS No. [86508-42-1].

[0037] The density of particles in solvent (solids content) may be anylevel at which the dispersion is stable and does not significantlycoagulate. For use of the latex in an electrophoretic display, thesolids content may be any level that allows proper functioning overrepeated cycles. Preferably, the solids content is less than 10 wt %,more preferably less than 5 wt %, and most preferably less than 2 wt %.

[0038] The latexes according to the present invention may beincorporated into electrophoretic displays. A typical display comprisestwo planar electrodes defining a thin gap between them which holds thelatex. When a sufficient voltage of the correct polarity is applied, thesuspended particles are drawn out of suspension and onto one electrode.That electrode, which is substantially transparent, forms the innersurface of a viewing glass, such that the particles form an image viewedthrough the glass. In contradiction to the characteristics of anelectrostatic toner, which must form a permanent image under analogousconditions, the latex of the present invention must return to suspensionwhen the voltage is removed or reversed.

[0039] The latexes of the present invention have high resistance to filmformation when used in electrophoretic display devices. To determineresistance to film formation, an actual device may be used or abreadboard device as described in the examples below. Latexes of anysolids content may be tested but preferably the solids content is 1 wt%. The device is preferably used in a normal manner, alternatelyapplying and removing (or reversing) the typical use voltage. Thevoltage should be sufficient to remove particles from suspension andcreate an image when applied. Preferably the latexes arenon-film-forming to the extent that they redisperse completely (byappearance to the naked eye) after at least twenty cycles, morepreferably after at least 100 cycles, and most preferably after at least10,000 cycles. Without wishing to be bound by theory, it is believedthat the resistance to film formation demonstrated by the latexes of thepresent invention is aided by incorporation of crosslinkers, by thechoice of high Tg monomers such as 3,4 methyl styrene, isobornylacrylate, by reduction of the fluoropolymer content resulting in athinner outer shell zone, by increasing the electrostatic charge(conductance) of the particles, by exclusion of particulate pigments,which may be replaced with dyes. The latexes and particles according tothe present invention are preferably non-film-forming due to one or moreof the preceding conditions.

[0040] Any suitable method of synthesis which results in the latexesaccording to the present invention may be used. One method of makinglatexes according to the present invention is illustrated by thesyntheses of latexes L1 to L15 in the Examples below. In this method, ahighly fluorinated macromer is synthesized by polymerization and themacromer is then derivatized to add a terminal polymerizable group. Themacromer is then polymerized together with non-fluorinated monomers,preferably using a polymerization initiator and optionally acrosslinker, to form the latex particle. Reacting dyes must be addedprior to polymerization. Non-reacting dyes and charging agents may beadded at any stage, but are preferably added prior to polymerization.All reactions preferably take place in a highly fluorinated solvent.Preferably the reaction mixture is no more concentrated than 15 wt %reactants relative to the amount of solvent.

[0041] A more preferred method of making the latexes of the presentinvention is designated the seed method, and is illustrated by thesyntheses of latexes L16 to L18 in the Examples below. In this methodthe polymerization to form the latex particles is performed in twosteps. First, the highly fluorinated macromer and a fraction of thenon-fluorinated monomers are polymerized with agitation to form apopulation of seed particles. The weight ratio of highly fluorinatedmacromer to non-fluorinated monomer is preferably between 1:2 and 9:1.In the second step, the remainder of the non-fluorinated monomers areadded. The amount of additional monomer is preferably at least 10% ofthe weight of the seed particles, and preferably not more than 20 timesthe weight of the seed particles. Preferably the reaction mixture is nomore concentrated than 15 wt % reactants relative to the amount ofsolvent. The seed method can achieve a smaller average particlediameter, preferably 250 nm or less, and more preferably 200 nm or less.

[0042] This invention is useful in electrophoretic image displays.

[0043] Objects and advantages of this invention are further illustratedby the following examples, but the particular materials and amountsthereof recited in these examples, as well as other conditions anddetails, should not be construed to unduly limit this invention.

EXAMPLES

[0044] Materials

[0045] The following materials were used in these examples. Where nototherwise noted, all chemicals and reagents may be available fromAldrich Chemical Co., Milwaukee, Wis.

[0046] TRIGONOX™ 21C-50 (50%) is a trade designation for a thermal freeradical polymerization initiator available from Akzo Nobel Chemicals,Inc., Watertown, Conn.

[0047] FLUORINERT™ materials are fluorinated solvents available from 3MCompany, St. Paul, Minn. FLUORINERT FC-75 is a perfluorinated C₈solvent, CAS No. [86508-42-1]. FLUORINERT FC-84 is a perfluorinated C₇solvent, CAS No. [86508-42-1].

[0048] FLUORAD™ materials are fluorinated surfactants/surface modifiersavailable from 3M Company, St. Paul, Minn. FLUORAD FC-740 is 50%fluoroaliphatic polymeric esters in naphtha, CAS No. [64742-94-5].FLUORAD FC-171 is a mixture of 87-93% fluorinated alkylalkoxylate, CASno. [68958-61-2]; 4-10% fluorinated alkylsulfonamide, CAS no.[4151-50-2]; and 2-4% fluorinated alkylsulfonamide, CAS no.[68958-60-1]. FLUORAD FC-722 is a 2% solution of fluorinated copolymerin perfluorinated C₅₋₁₈ solvent, CAS No. [86508-42-1]. FLUORAD FC-430 isa 98.5% solution of fluoroaliphatic polymeric esters in toluene. FLUORADFC-189 is 2-(N-butylperfluorooctanesulfonamido) ethyl acrylate. FLUORADFC-170C is 68 wt % perfluoroalkylsulfonamido oxyethylene adduct[29117-08-6], 12 wt % polyethylene glycol, 7 wt % water, approx. 5 wt %perfluoroalkylsulfonamido oxyethylene adduct [56372-23-7], and approx. 5wt. % perfluoroalkylsulfonamido oxyethylene adduct [68298-79-3].

[0049] Lithium bis(trifluoromethylsulfonyl)amide is available under thetrade designation HQ-115 from 3M Company, St. Paul, Minn.

[0050] 1H,1H-perfluoroalkyl methacrylate is available under the tradedesignation L-1987 from 3M Company, St. Paul, Minn.

[0051] 1H,1H-perfluorooctyl acrylate is available from Exfluor Corp.,Austin, Tex.

[0052] PEG (400) diacrylate is a polyethylene glycol diacrylateavailable from Polysciences, Inc., Los Angeles, Calif.

[0053] Dibutyltin dilaurate, isocyanatoethyl methacrylate, vinyltrifluoroacetate, 3-mercapto-1,2-propanediol,2,2′-azobis(isobutyronitrile), isobornyl methacrylate, methylmethacrylate, ethyl methacrylate, 1-ethyl-3-methyl-1H-imidazoliumchloride, 2,2,2-trifluoroethyl acrylate, and dimethylaminoethylmethacrylate are available from Aldrich Chemical Co., Milwaukee, Wis.and other general chemical suppliers.

[0054] Mercaptopropyltrimethoxysilane was obtained from United ChemicalTechnologies, Inc., Petrarch Systems, Bristol, Pa.

[0055] OXSOL™ R 2000 is α,α,α-trifluoromethyltoluene, available fromOccidental Chemical Corp., Dallas, Tex.

[0056] FLUORAD™ FC-3275 is a blue dye in perfluorinated C₇-C₈ solventsavailable from 3M Company of St. Paul, Minn.

[0057] GENSOLVE™ 2000 is dichlorofluoromethane CAS No. 1717-00-6; alsolabeled as hydrochlorofluorocarbon HCFA-141b.

[0058] Synthesis of Fluoromacromer Solvents with Polymerizable TerminalGroups

[0059] Fluorocarbon macromers designated FMD-1, FMD-2, FMD-3 and FMD-4,were synthesized using the components listed in Table I and theprocedure described following.

[0060] A mixture of the monomers indicated in Table I was dissolved inthe indicated solvent (Fluorinert™ FC-75 or FC-84) to make a 50% (byweight) solution, in a three-neck flask equipped with a refluxcondenser, nitrogen inlet tube and addition funnel. The specified amountof 3-mercapto-1,2-propanediol was added as a chain transfer agent. Themixture was flushed with nitrogen for 20 minutes. The specified amountof the indicated polymerization initiator (Trigonox 21C-50 or2,2′-azobisisobutyronitrile) was added. The mixture was then polymerizedfor 12 hrs at 75° C. A second increment of the initiator in the sameamount was added and the mixture was polymerized for another 12 hrs at75° C. Next, the reaction temperature was raised to 85° C. for 1 hr todestroy residual initiator. The polymer dispersion was then cooled toroom temperature.

[0061] Finally, the terminal group monomer, isocyanatoethyl methacrylate(IEM), was added with thorough mixing in the indicated amount, which isstoichiometrically equimolar to the chain transfer agent, followed bytwo drops of dibutyltin dilaurate to complete the reaction of theisocyanate with one of the two hydroxyl end groups of the polymer. TABLEI FMD-1 FMD-2 FMD-3 FMD-4 Fluorinert ™ Solvent FC-84 FC-84 FC-75 FC-75Monomers: 1H,1H-Perfluoroalkyl  93.6 g methacrylate 1H,1H-Perfluorooctyl136.23 g 136.23 g 136.23 acrylate FLUORAD ™ FC-189  45.4 g  45.4 g  31.2g Dimethylaminoethyl  13.6 g methacrylate Vinyl trifluoroacetate   25 g2,2,2-trifluoroethyl acrylate   25 g Chain Transfer Agent: 0.3225 g0.3225 g   0.2 g 0.215 g 3-mercapto-1,2-propanediol Initiators:Trigonox ™ 21C-50    1 g    1 g   0.5 g  0.32 g2,2′-azobisisobutyronitrile  0.33 g Terminal Group Monomer:  0.925 g 0.925 g  0.60 g  0.62 g Isocyanatoethyl meth- acrylate

[0062] Synthesis of Charging Agent, 1-ethyl-3-methyl-1H-imidazoliumbis(trifluoromethylsulfonylamide)

[0063] 1-Ethyl-3-methyl-1H-imidazolium chloride (49.0 g) was dissolvedin 285.0 g deionized water to form a 1M solution. 127.8 ml of thissolution was combined with 36.7 g lithiumbis(trifluoromethylsulfonyl)amide and 50 ml dichloromethane in a flaskwith a magnetic stir bar. The solution was allowed to stir overnight,then transferred to a separatory funnel, where the aqueous phase waswashed three times with 10 ml of dichloromethane. The threedichloromethane phases were combined and the dichloromethane was removedunder reduced pressure. The recovered material was used without furtherpurification.

[0064] Synthesis of Non-Film Forming White Acrylic Latex Particles

[0065] White (non-dye-bearing) acrylic latexes, designated L1, L2, L3,L4 and L5, were synthesized using the components listed in Table II andthe procedure described following.

[0066] A mixture of the indicated acrylic monomers, optionally includingPEG 400 diacrylate crosslinker as indicated, was suspended in 500 ml ofFluorinert™ solvent FC-75 along with the indicated fluoromacromersolvent, FMD-1 or FMD-4, in a three-neck flask equipped with a refluxcondenser, nitrogen inlet tube and addition funnel. Where indicated, amixture of the indicated Fluorad™ surfactants was added to enhance thestability of the dispersion. Where indicated, a charging agent,1-ethyl-3-methyl-1H-imidazolium bis(trifluoromethylsulfonylamide), wasadded. A polymerization initiator, Trigonox™ 21C-50, was added in anamount of 0.1-0.2% by weight of the reaction mixture. This reactionmixture was flushed with nitrogen for 20 minutes and then the mixturewas polymerized for 12 hrs at 75° C. A second increment of the initiatorin the same amount was added and the mixture was polymerized for another12 hrs at 75° C. The resulting latex was then filtered through a thicklyfolded cheese cloth to remove agglomerated particles.

[0067] The resulting latexes contained a solids content of about 5 wt %.Solids content was measured by evaporating a known weight of the latexto dryness by heating to 100° C. in a vacuum oven and weighing of theremaining dry solids.

[0068] Particle size and size distribution, reported in Table II, weremeasured using a Coulter N4 PLUS dynamic light scattering photometer(Coulter Corp., Miami, Fla.) with a measuring range of 3 nm to 3 μm.Particle size and size distributions were obtained at the high dilutionrange set by the instrument.

[0069] Conductance, reported in Table II, was measured using aScientifica Model 627 conductivity meter (available from Scientifica ofPrinceton, N.J.) using a stainless steel concentric cylinder probe. Afrequency of 18 Hz was applied to the outer cylinder. The conductivityof the liquid sample was determined by measuring the current between theouter cylinder and the inner cylinder. Higher conductance is indicativeof higher charge/mass ratio, which indicates that the particles may bemore easily moved by application of an electric field.

[0070] Film-forming characteristics were tested in a breadboard displaydevice, which included a transparent indium tin oxide electrode coatedon an essentially planar high refractive index display glass opposite anessentially planar metal counter electrode. The gap between electrodeswas 5-10 μm. The volume between the display glass electrode and thecounter electrode was filled with the latex to be tested and a voltageof 10 volts was applied for less than a second, driving the latexparticles to the display glass. After the voltage was removed,non-film-forming latexes redispersed in the solvent, whereasfilm-forming latexes fully or partially remained on the display glass.Non-film-forming latexes redisperse completely (by appearance to thenaked eye) after at least twenty cycles. Film forming latexes typicallywould not rediperse in the first or second cycle. Toner compositions areunable to redisperse after a single cycle, consistent with their role inelectrophotographic processes.

[0071] Latexes L1-L5 were found to be non-film forming. TABLE II L1 L2L3 L4 L5 Monomers: Ethyl Methacrylate  20 g   15 g Methyl Methacrylate 20 g   15 g Isobornyl   20 g 20 g Methacrylate PEG 400 Diacrylate  4 g 4 g FC Macromer: FMD-4 12.5 g FMD-1  1.5 g  1.5 g 12.5 g 15 gSurfactant Mixture: none none FC-430, 2 g FC-740, 0.6 g FC-430, 2.0 gFluorad ™ surfactants FC-170C, 3 g FC-171, 0.5 g FC-170C, 2.5 g FC-722,2.5 g Charging Agent: none none  0.5 g  0.5 g none Conductance 1.74 4.89.5 4.5 9.5 (picomho/cm) Particle Size 302 nm 575 nm 800 nm 280 nm notmeasured {distribution} {narrow} {broad} {broad} {narrow}

[0072] Addition of Charging Agent to Non-Film Forming Acrylic LatexParticle Dispersions

[0073] Acrylic latexes L1, L2, L4 and L5 were diluted to 1 wt %dispersions in FC-75 solvent. Additional charging agent was added to thedispersion in the amount indicated and the conductivity was measured bythe method described above. TABLE III L1 L2 L4 L5 Conductance(picomho/cm) No additional charging agent 1.74 4.8 4.6 9.5 0.02%additional charging agent 1.83 4.4 4.6 9.3 0.04% additional chargingagent 1.85 4.3 4.7 9.2 0.10% additional charging agent 902 220 550 1398

[0074] Synthesis of Non-Film Forming Dye-Bearing Acrylic Latex Particles

[0075] Dye-bearing acrylic latexes, designated L6 (Cyan), L7 (Cyan), L8(Red), L9 (Yellow), L10 (Yellow), L11 (Violet), L12 (Magenta), L13(Cyan) and L14 (Magenta), were synthesized using the components listedin Table IV and the procedure described following.

[0076] A mixture of the indicated acrylic monomers, optionally includingPEG 400 diacrylate crosslinker as indicated, was suspended in 500 ml ofFluorinert™ solvent FC-75 along with 2.0 g of fluoromacromer solventFMD-1. (IBA=isobornyl acrylate, MMA=methyl methacrylate, EMA=ethylmethacrylate). For L6 (Cyan) only, 3 g of a mixture of Fluorad™surfactants (2:3 by weight FC-430 and FC-171) was added to enhance thestability of the dispersion. The indicated hydrocarbon-soluble dye wasdissolved in the monomer mixture along with a small quantity ofGenesolve™ 2000 (essentially CH₃CCl₂F; Allied Signal, Morristown, N.J.)to facilitate and accelerate the solvation of the dye. A polymerizationinitiator, Trigonox™ 21C-50, was added in an amount of 0.1-0.2% byweight of the reaction mixture. This reaction mixture was flushed withnitrogen for 20 minutes and then the mixture was polymerized for 12 hrsat 75° C. A second increment of the initiator in the same amount wasadded and the mixture was polymerized for another 12 hrs at 75° C. Theresulting latex was then filtered through a thickly folded cheese clothto remove agglomerated particles.

[0077] Dyes were modified as follows:

[0078] PECHS salts of Basic Violet (C.I. 42555) and Basic Blue (C.I. 1)were made by exchanging cations for PECHS:

[0079] Derivatized Solvent Yellow 18 (C.I. 12740) was a reactive dyeincorporating a function polymerizable with the acrylic monomers. Thederivatized dye was made as follows: 1 g of Solvent Yellow 18 (C.I.12740) was suspended in ˜25 ml of FC-75 perfluorinated fluid bysonication. Isocyanatoethyl methacrylate (0.566 g) was added dropwise tothe dye suspension under sonication, followed by two drops of dibutyltindilaurate catalyst. After an hour under sonication and agitation, thesuspension was filtered, washed with FC-84 and dried under vacuum below40° F., the dry solid being the derivatized dye.

[0080] It was found that the dyes were substantially entirely containedin the latex particles, presumably in the hydrocarbon polymer core.Unreacted dye was found in a coagulum obtained after filtering the latexthrough cheesecloth as described.

[0081] The resulting latexes contained a solids content of about 5 wt %,measured as described above.

[0082] Particle size and conductance were measured as described above.Latexes L6-L14 were each tested and proved to be non-film forming. TABLEIV L12 L14 L10 L6 (Cyan) L7 (Cyan) L11 (Violet) L13 (Cyan) L8 (Red)(Magenta) (Magenta) L9 (Yellow) (Yellow) Dye 0.25 g 0.25 g 0.2 g Basic0.2 g Basic 0.2 g 0.2 g 0.2 g 1.6 g 1.75 g Solvent Solvent Violet Blue(C.I. 1) Solvent Red Magenta Magenta Derivatized Derivatized Blue Blue(C.I. 97) (C.I. 42555) PECHS salt 23 (C.I. 26100) Solvent Dye SolventDye Solvent Solvent (C.I. 97) PECHS salt (CAS (CAS Yellow 18 Yellow 1858559-02-7) 58559-02-7) (C.I. 12740) (C.I. 12740) Monomer  25 g MMA  25g MMA  25 g MMA  25 g MMA  25 g IBA  25 g MMA  25 g MMA  25 g EMA  25 gMMA Crosslinker: None  5 g  5 g  5 g  5 g  5 g  5 g None  5 g 5 g PEG(400) diacrylate Conductance 1.0 3.4 2.4 3.8 44 2.5 2.8 4.5 1.7(picomho/cm) Particle Size 255 nm 290 nm 300 nm 240 nm 240 nm 280 nm 300nm 300 nm 260 nm (distribution) (narrow) (narrow) (narrow) (narrow)(narrow) (narrow) (narrow) (narrow) (narrow)

[0083] Synthesis of Very Fine Non-Film Forming White Acrylic LatexParticles by Seed Method

[0084] A latex of very fine white (non-dye-bearing) acrylic particles,designated L16, was synthesized using the seed method describedfollowing.

[0085] 2.5 g of FMD-1 and 2.5 g methylstyrene (a mixture of 3- and4-methyl isomers obtained from Aldrich Chemical Company, Milwaukee,Wis., Cat. No. 30,898-6) were added to 250 ml of Fluorinert™ solventFC-75, in a three-neck flask equipped with a reflux condenser, nitrogeninlet tube and addition funnel. One gram of the polymerizationinitiator, Trigonox™ 21C-50, was added. This reaction mixture wasflushed with nitrogen for 15 minutes and then the mixture waspolymerized for about 100 minutes at 80° C. with vigorous stirring usinga magnetic stir bar. A white turbid suspension of seed polymer particlesresulted. The temperature of the reaction mixture was lowered to 70° C.with continued stirring and another 1 part Trigonox™ 21C-50 was added.An additional 10 g of the methylstyrene was added dropwise via anaddition funnel into the stirred reaction mixture over a period of 2hours while the reaction temperature was kept at 70° C. After additionof monomer was complete the polymerization was allowed to continue foranother 16 hours. The resulting latex was then filtered through athickly folded cheese cloth to remove agglomerated particles. The latexhad an average particle size of 220 nm and a conductance of 0.1picomho/cm, measured as described above.

[0086] Synthesis of Very Fine Non-Film Forming Dye-Bearing Acrylic LatexParticles by Seed Method

[0087] The synthesis of L16, preceding, was repeated except that 0.15 gof Solvent Blue (C.I. 97) dye were dissolved in the 10 g ofmethylstyrene monomer added dropwise to the seed suspension. Theresulting cyan colored latex, designated L17 (Cyan), had an averageparticle size of 375 nm; and a conductance of 0.1 picomho/cm, measuredas described above.

[0088] Additional Synthesis of Very Fine Non-Film Forming Dye-BearingAcrylic Latex Particles by Seed Method

[0089] The synthesis of very fine dye-bearing latex L18 (Cyan), usingthe seed method described following, was repeated three times.

[0090] In a reaction flask, 7.5 g of FMD-1 and 2.5 g ethyl acrylate wereadded to 250 parts ml of Fluorinert™ solvent FC-75, in a three-neckflask equipped with a reflux condenser, nitrogen inlet tube and additionfunnel. One gram of the polymerization initiator, Trigonox™ 21C-50, wasadded. This reaction mixture was flushed with nitrogen for 30-45minutes. The temperature was rapidly raised to 80° C. and then themixture was polymerized for 2 hrs with vigorous stirring using amagnetic stir bar. After two hours, a mixture of 10 g of isobornylacrylate and 0.2 g of Solvent Blue (C.I. 97) dye was added dropwise viaan addition funnel into the stirred reaction mixture over a period of 1hour while the reaction temperature was kept at 70° C. An additional 1 gof Trigonox™ 21C-50 was added. After addition of monomer was completethe polymerization was allowed to continue for another 16-20 hours. Theresulting latex was then filtered through a thickly folded cheese clothto remove agglomerated particles. Particle size and conductance weremeasured as described above. In three repetitions of this synthesis, thethree resulting latexes were found to have average particle sizes of140, 160 and 175 nm respectively. Conductance was measured as 0.79picomho/cm for one of the L18 (Cyan) latexes.

[0091] Synthesis of Perfluoropolyether Fluoromacromer Dispersant

[0092] A fluoromacromer dispersant designated FMD-5 based on aperfluoropolyether was synthesized as follows.

[0093] The perfluoroether diol HO—CH₂CF₂—O—(CF₂CF₂O)_(n)—CF₂CH₂—OH wassynthesized, where n is a distribution (nominally 10) and the diol hasan average molecular weight of 1250. Polyethylene glycol (ave. m.w. 600)(Aldrich Chemical Co., Milwaukee, Wis.) was mixed with approximately twoequivalents of CH₃C(O)Cl at ambient temperature in the presence of twoequivalents of triethylamine to form a diacetate. The diacetate was thenfluorinated by direct fluorination, such as disclosed in U.S. Pat. No.4,523,039 (Lagow et al.). The resulting fluorinated acetate was mixedwith excess amount of methanol whereupon it reacted to give methylesters such as CH₃O(CO)CF₂O—(CF₂CF₂O)_(n−2)—CF₂(CO)OCH₃. These methylesters were then reduced to the corresponding dihydroalcohols, such asHOCH₂CF₂O—(CF₂CF₂O)_(n−2)—CF₂CH₂OH, by reaction with approximately twoequivalents of NaBH₄. The resulting mixture was distilled under reducedpressure and a 1250 m.w. fraction collected.

[0094] To 35 g of this perfluoroether diol (m.w. 1250) in a coveredamber jar was added dropwise 4.34 g (aprox. 1 equivalent) ofisocyanatoethyl methacrylate (m.w. 155) to obtain a milky liquid. Whenthe milky liquid turned clear, indicating the completion of the reactionbetween the hydroxyl and isocyanate, two drops of dibutyltin dilauratewere added to the reaction mixture.

[0095] Synthesis of Acrylic Latex Particles Using FMD-5Perfluoropolyether Fluoromacromer

[0096] Acrylic latexes designated L19 (Cyan) and L20 (Near-White) weresynthesized as follows.

[0097] For L19(Cyan), 5 g of FMD-5 was combined with 12.5 gmethylstyrene (a mixture of 3- and 4-methyl isomers obtained fromAldrich Chemical Company, Milwaukee, Wis., Cat. No. 30,898-6), 5 g ofGensolve™ 2000, 0.2 g Solvent Blue (C.I. 97) and 250 g of Fluorinert™solvent FC-75, in a three-neck flask equipped with a reflux condenser,nitrogen inlet tube and addition funnel. A polymerization initiator,Trigonox™ 21C-50, was added in the amount of 1 g. This reaction mixturewas flushed with nitrogen for 30 minutes and then the mixture waspolymerized for 6 hrs at 75° C. A second increment of the initiator inthe same amount was added and the mixture was polymerized for another 20hrs at 75° C. The resulting latex was then filtered through a thicklyfolded cheese cloth to remove agglomerated particles.

[0098] The resulting cyan colored latex, designated L19 (Cyan), had anaverage particle size of 172 nm, measured as described above.

[0099] For L20 (Near-White), the same procedure was followed except thatthe cyan dye was replaced with 0.2 g of Magenta Solvent Dye (CAS58559-02-7). The resulting latex, designated L20 (Near-White), was anear-white pale pink color and had an average particle size of 170 nm,measured as described above.

[0100] Both L19 (Cyan) and L20 (Near-White) are observed to benon-film-forming.

[0101] Various modifications and alterations of this invention willbecome apparent to those skilled in the art without departing from thescope and principles of this invention, and it should be understood thatthis invention is not to be unduly limited to the illustrativeembodiments set forth hereinabove. All publications and patents areherein incorporated by reference to the same extent as if eachindividual publication or patent was specifically and individuallyindicated to be incorporated by reference.

We claim:
 1. A compound according to the formula:CH₂═C(R¹)—C(O)—R⁶—NHCO₂(CH₂)_(p)(CF₂)_(q)—O—((CF₂)_(a)CFXO)_(m)(CF₂)_(r)—Zwherein each R¹ is independently selected from —H, —CH₃, —F and —Cl,wherein each R⁶ is independently selected from substituted orunsubstituted C1-C10 alkyl, cyclic alkyl, or aryl groups, wherein each ais independently selected from 0-3, wherein each X is independentlyselected from —F, —CF₃ or —CF₂CF₃, wherein each p is independentlyselected from 1-4, each q is independently selected from 1-5, each r isindependently selected from 1-5, each m is independently selected from1-50, each Z is independently selected from —F and —(CH₂)_(s)OH, whereeach s is independently selected from 1-4.
 2. The compound according toclaim 1 wherein each m is independently selected from 7-15.
 3. Thecompound according to claim 2 wherein Z is —(CH₂)_(s)OH, wherein a, p,q, r and s are each 1 and wherein X is —F.
 4. A solution of the compoundaccording to claim 1 in a highly fluorinated solvent.
 5. A solution ofthe compound according to claim 2 in a highly fluorinated solvent.
 6. Asolution of the compound according to claim 3 in a highly fluorinatedsolvent.
 7. A second compound which is a reaction product of thecompound according to claim 1 resulting from free-radical addition tothe ethylenic double bond.
 8. A second compound which is a reactionproduct of the compound according to claim 2 resulting from free-radicaladdition to the ethylenic double bond.
 9. A second compound which is areaction product of the compound according to claim 3 resulting fromfree-radical addition to the ethylenic double bond.
 10. A stablesuspension of the second compound according to claim 7 in a highlyfluorinated solvent.
 11. A stable suspension of the second compoundaccording to claim 8 in a highly fluorinated solvent.
 12. A stablesuspension of the second compound according to claim 9 in a highlyfluorinated solvent.
 13. A non-film-forming latex of particlescomprising the second compound according to claim 7 in a highlyfluorinated solvent.
 14. A non-film-forming latex of particlescomprising the second compound according to claim 8 in a highlyfluorinated solvent.
 15. A non-film-forming latex of particlescomprising the second compound according to claim 9 in a highlyfluorinated solvent.